種々のハロゲンアルカンの遊離基的還元 : 水素化有機ケイ素化合物を用いる還元反応(第2報)

概要

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Reduction of a variety of haloalkanes with organosilicon hydrides was carried out under homolytic conditions. While the fluorides and iodides employed were found to be quite inert, the bromides and chlorides could be readily reduced. The mode of the reduction is consistent with a radical chain mechanism previously proposed. The apparent reactivities (Br>Cl>>F, I) can be reasonably understood by applying the Hirschfelder rules to the halogen atom abstraction step in the presence of the organosilyl radicals. The vicinal dibromide underwent radical debromination rather than bromine-hydrogen exchange, presumably due to the reversible addition of bromine atoms to olefins. Simple alkyl bromides, however, are less reactive than carbon tetrachloride. This seems to imply that the polar factor is also important in determining the relative rates of the halogen atom abstraction.
社団法人有機合成化学協会の論文